1283706 A7 B7 五、發明説明“) 技術領域 (請先閲讀背面之注意事項再填寫本頁) 本發係有關洗淨硏磨襯墊用組成物及硏磨襯墊之洗淨 方法。詳細的說，係有關使用於硏磨之硏磨襯墊於硏磨時 抑制水不溶性化合物形成而產生阻塞及硏磨襯墊的消耗， 更能恢復硏磨效率的洗淨硏磨襯墊用組成物及使用此洗淨 研1磨襯墊用組成物的硏磨襯墊之洗淨方法。 先行技術 經濟部智慧財產局員工消費合作社印製 使用於半導體基板的硏磨的化學機械硏磨（以下以「 CMP」稱之），於硏磨襯墊與被硏磨面的界面供給含硏 磨粒的漿狀物（水系分散物）進行硏磨。此時，係使用聚 氨基甲酸乙酯發泡物等的多孔物作爲硏磨襯墊，因硏磨屑 等逐漸阻塞，降低硏磨速度。因此，爲恢復硏磨襯墊的表 面使其適於C Μ P，進行硏磨面更新的打磨步驟。此打磨 步驟係以附著鑽石粉末等的硏磨物（打磨物）摺動硏磨襯 墊表面。已知的此打磨步驟有稱爲in situ打磨方法，及 interval打磨方法。前者係硏磨進行中打磨硏磨襯墊上無 硏磨的範圍的方法，後者爲停止硏磨進行打磨的方法。 現今的C Μ P係因應必要而進行in situ打磨，interval 打磨則通常爲必須者。此時，每硏磨一片被硏磨物進行5 〜3 0秒interval打磨。因此，提高製品的收率有一定的 界限。更進一步，interval打磨僅明顯的進行物理的及供 給冷卻用水。但是，並未試以倂用化學的的效果。 近年，曰本特開2000 — 309796號公報揭示 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐） -4- 1283706 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（2 ) 在interval打磨時使用含陰離子性的界面活性劑的洗淨劑 組成物的技術。但是，此洗淨劑組合物無關被硏磨物的種 類，可廣泛使用硏漿，一方面依構成半導體基板的成分、 硏漿中所含的成分，難以爲最適宜的洗淨劑組成物。 又，作爲C Μ P使用的硏漿，如日本特開平 8 — 83780號公報，曰本特開平10 — 1 16804 號公報，日本特開平11—116948號公報及日本特 開平2 0 0 1 - 1 1 0 7 5 9號公報所揭示，爲防止構成 被硏磨面的金屬因硏漿而被過度浸蝕爲目的，或防止已硏 磨的金屬再度附著於硏磨面的目的等，提案使用以硏漿中 含形成被硏磨面分離的金屬原子或其離子的水不溶物成分 的硏漿。 使用如此的硏漿解消C Μ Ρ用硏磨襯墊的阻塞，僅以 向來的interval dressing及in situ dressing 的機械處理時有 困難，interval dressing比向來的所需的時間長，僅進行長 時間dressing硏磨襯墊的消耗亦激烈，不理想。 發明揭示 本發明係提供爲解決上述問題，至少可洗淨一部份硏 磨中形成於硏磨襯墊表面的水不溶物，可恢復硏磨速度， 更可抑制硏磨襯墊的消耗的洗淨硏磨襯墊用組成物爲目的 。又，提供使用如此的洗淨硏磨襯墊用組成物更有效率的 進行硏磨襯墊的洗淨，可提高生產性，更可抑制磨墊的消 耗的硏磨襯墊的洗淨方法爲目的。 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5- 1283706 A7 B7 _ 五、發明説明（3 ) 本發明如以下所述。 (請先閲讀背面之注意事項再填寫本頁) 1.含有可以水溶化由被硏磨面分離之金屬原子或其 離子之水不溶性化合物之水溶化成分爲特徵的洗淨硏磨襯 墊用組成物。 2 ·上述水溶化成分係由氨、氫氧化鉀、氫氧化四甲 基銨、氫氧化三甲基- 2 -經乙基銨、氫氧化甲基三羥乙 基銨、氫氧化二甲基二羥基銨、氫氧化四乙基銨及氫氧化 三甲基乙基銨中選取之至少一種之上述1所記載之洗淨硏 磨襯墊用組成物。 3 .上述金屬係由銅、鋁、鎢及鉅中選取之至少一種 之上述2所記載之洗淨硏磨襯墊用組成物。 4 .更含有與上述金屬原子或其離子形成水可溶性配 位化合物之水可溶性配位化合物形成成分之上述1所記載 之洗淨硏磨襯墊用組成物。 經濟部智慧財產局員工消費合作社印製 5 .上述水溶化成分係由由氨、氫氧化鉀、氫氧化四 甲基銨、氫氧化三甲基- 2 -羥乙基銨、氫氧化甲基三經 乙基銨、氫氧化二甲基二羥基銨、氫氧化四乙基銨及氫氧 化三甲基乙基銨中選取之至少一種之上述4所記載之洗淨 硏磨襯墊用組成物。 6 .上述水可溶性配位化合物形成成分，係具二個以 上官能基可與上述金屬原子及其離子配位的上述5所記載 之洗淨硏磨襯墊用組成物。 7 .上述水可溶性配位化合物形成成分，係由甘氨酸 、丙氨酸、半胱氨酸、醯胺硫酸、乳酸、檸檬酸、酒石酸 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -6- 1283706 A7 B7 五、發明説明（4 ) '蘋果酸、丙二酸、草酸、琥珀酸、富馬酸及馬來酸中選 取之至少一種之上述6所記載之洗淨硏磨襯墊用組成物。 8 ·上述金屬係由銅、鋁、鎢及钽中選取之至少一種 t ±述7所記載之洗淨硏磨襯墊用組成物。 9·附著含有由被硏磨面分離的金屬原子或離子的水 不溶性化合物的硏磨襯墊洗淨方法，與含水溶化上述水不 溶性化合物的水溶化成分的洗淨硏磨襯墊用組成物接觸爲 特徵的硏磨襯墊洗淨方法。 10.上述水溶化成分係由氨、氫氧化鉀、氫氧化四 甲基銨、氫氧化三甲基一 2 -羥乙基銨、氫氧化甲基三羥 乙基銨、氫氧化二甲基二羥基銨、氫氧化四乙基銨及氫氧 化三甲基乙基銨中選取之至少一種之上述9所記載之硏磨 襯墊洗淨方法。 1 1 .上述金屬係由銅、鋁、鎢及钽中選取之至少一 種之上述1 0所記載之硏磨襯墊洗淨方法。 經濟部智慧財產局員工消費合作社印製 12. 更含有與上述金屬原子或其離子形成水可溶性 配位化合物之水可溶性配位化合物形成成分之上述9所記 載之硏磨襯墊洗淨方法。 13. 上述水溶化成分係由氨、氫氧化鉀、氫氧化四 甲基銨、氫氧化三甲基- 2 -羥乙基銨、氫氧化甲基三羥 乙基銨、氫氧化二甲基二羥基銨、氫氧化四乙基銨及氫氧 化三甲基乙基銨中選取之至少一種之上述12所記載之硏 磨襯墊洗淨方法。 1 4 .上述水可溶性配位化合物形成成分，係具二個 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐） 1283706 A7 B7 五、發明説明（5 ) 以上官能基可與上述金屬原子及其離子配位的上述1 3所 記載之硏磨襯墊洗淨方法。 (請先閲讀背面之注意事項再填寫本頁) 1 5 ·上述水可溶性配位化合物形成成分，係由甘氨 酸、丙氨酸、半胱氨酸、醯胺硫酸、乳酸、檸檬酸、酒石 酸、蘋果酸、丙二酸、草酸、琥珀酸、富馬酸及馬來酸中 選取之至少一種之上述1 4所記載之硏磨襯墊洗淨方法。 1 6 ·上述金屬係由銅、鋁、鎢及钽中選取之至少一 種之上述1 5所記載之硏磨襯墊洗淨方法。 依本發明的洗淨硏磨襯墊用組成物及硏磨襯墊之洗淨 方法，可解除使用於硏磨的硏磨襯墊由被硏磨面分離，已 離子化金屬離子所成的水不溶性化合物而形成的阻塞，可 恢復硏磨速度，抑制硏磨襯墊的消耗，更可提高生產性。 本發明的洗淨硏磨襯墊用組成物係含有水溶化成分可 水溶化由被硏磨面分離之金屬原子或其離子之水不溶性化 合物爲特徵。 經濟部智慧財產局員工消費合作社印製 上述「金屬」無特別限定，可列舉如銅、鋁、鎢、鉬 、鉅、鈦、銦及錫等，單1種此金屬，或2種以上均可’ 離子的價數亦無限制。使用於本發明的洗淨硏磨襯墊用組 成物的上述金屬中亦以由鋁、鎢及鉅中選取之至少一種時 特別有效果。 又，作爲構成金屬原子或其離子的分離源之上述「被 硏磨面」基材’可舉例如金屬的卓體或合金（銅-桂合金 及銅-鋁合金等）。由此被硏磨面分離之過程亦無特別限 制，由被硏磨面以含於硏漿中之酸或氧化劑等離子化後分 本紙張尺度適用中國國家標準（ CNS)A4規格（210x297公董^ 1283706 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（6 ) 離亦可，又，依後述含於硏漿中之水不溶性化合物形成成 分等結合後，以硏磨分離亦可。 作爲支持此硏磨面的基材，無特別限制可使用種種不 同基材，可例舉如半導體基板、L C D用玻璃基板及 T F T用玻璃基板等。 上述「水不溶性化合物」係硏磨中不溶解於硏漿等， 以固體成分殘留於硏磨襯墊的硏磨面之化合物。但是，亦 含非完全不溶解於水僅少許溶解於水的水難溶性化合物。 此水不溶性化合物的溶解度雖無特別的限制，通常指p Η 1〜1 2，溫度1 5〜5 0 °C之間的任意條件下，低於1 g/1 0 0 g水之化合物。特別是上述的金屬爲銅之pH 7〜1 1時，鋁之pH 2〜6時，鎢的pH2〜6時、钽 的PH3〜1 1時，各溶解度易成爲低於1 g/1 〇〇g 水。又，此水不溶性化合物爲1種或2種以上均可。 作爲形成此化合物的水不溶性化合物形成成分，無特 別限制，可列舉例如羥基、烷氧基（甲氧基、乙氧基等） 、羧基、羰基（甲氧基羰基、乙氧基羰基等）、氨基（含 第1級氨基、第2級氨基、第3級氨基、羥基氨基、硝基 氨基、亞硝基氨基等）、亞氨基（含肟基、羥基亞氨基、 磺基亞氨基、硝基工氨基、亞硝基亞氨基等）、氰基、氰 酸基、腈基、亞硝基、氮川基、磺基、磺醯基、亞磺基、 磺酸基、巯基、氨基甲醯基等（含水系媒體中有關此等的 離子）具備含氮、氧、硫官能基的化合物。更可列舉具備 此等官能基的芳香族化合物、或雜環化合物、或雜縮合環 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9- 1283706 Α7 Β7 五、發明説明（7 ) 化合物（特別是具雜五環的縮合環化合物或具雜六環的縮 合環化物）。 (請先閲讀背面之注意事項再填寫本頁) 作爲水不溶性化合物形成成分的具體例，可列舉如吡 嗪、吡啶、吡咯、噠嗪、組氨酸、噻吩、三氮雜環、甲苯 三氮雜環、吲哚、苯并咪唑、苯并三氮雜環、苯并呋喃、 苯幷噁唑、苯幷噻吩、苯并噻唑、喹啉、喹喔啉、喹唑啉 、對苯醌、苯幷啡啶、苯并吡喃、苯井噁嗪及密胺等的衍 生物化合物（特別是，具有上述官能基的衍生物化合物） 、水楊醛肟、銅鐵靈、磺酸等。 又，水不溶性化合物不單是如上述的水不溶性化合物 形成成分與銅的生成物，亦含由硏磨硏漿中所含氧化劑氧 化之氧化銅。 經濟部智慧財產局員工消費合作社印製 上述「水溶化成分」，係將上述不溶性化合物水溶化 的成分。由此水溶化成分，水不溶性化合物經由硏磨襯墊 表面滴入的水或由硏磨襯墊的水浸漬，充分的以水溶解爲 理想。有關此類水溶化成分可列舉如氨、氫氧化鉀及氧化 第4級銨{氫氧四甲基銨（TMAH)、氫氧化三甲基一 2 -羥乙基銨、氫氧化甲基三羥乙基銨、氫氧化二甲基二 經基銨、氫氧化四乙基銨、氫氧化三甲基乙基銨等丨（含 有關水系媒體中此類的離子）等。其中，以使用氨及/或 T M A Η爲理想。可單獨使用一種此類水溶化成分，或二 種以上混合使用亦可。 又，此類的水溶化成分，至少具1種上述金屬銅、銘 、鎢、鉅時，可有效果的水溶化此化合物，上述金屬爲銅 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -10 - 1283706 A7 B7 五、發明説明（8 ) 時特別理想。 (請先閱讀背面之注意事項再填寫本頁) 本發明洗淨硏磨襯墊用組成物含有此水溶化成分的量 雖無特別限制，，本發明洗淨硏磨襯墊用組成物全體爲 1 00質量％時，以0 . 0 1〜20質量％ (理想爲 0 . 1〜15質量％，更理想爲0 · 5〜10質量％)爲 理想。 又，本發明的洗淨硏磨襯墊用組成物，更以含有金屬 原子或其離子與形成水可溶性配位化合物的水可溶性配位 化合物形成成分爲理想。 上述「水可溶性配位化合物」對水具易溶性，可充分 的溶解於水的配位化合物。此水可溶性配位化合物的溶解 度，以同樣測定條件，超過水不溶性化合物的溶解度者， 無特別限制。又，此配位化合物可爲1種或2種以上均可 〇 經濟部智慧財產局員工消費合作社印製 上述「水可溶性配位化合物形成成分」係與金屬離子 配位形成水可溶性配位化合物的成分。通常此水可溶性配 位化合物形成成分，具與金屬離子配位的官能基。此官會g 基至少含氮、氧、硫中之任一者爲理想。此類官能基可歹[j 舉如羥基、烷氧基（甲氧基、乙氧基等）、羧基、羰基（ 甲氧基羰基、乙氧基羰基等）、氨基（含第1級氨基、第 2級氨基、第3級氨基、羥基氨基、硝基氨基、亞硝基氨 基等）、亞氨基（含B基、經基亞氨基、磺基亞氨基、硝 基工氨基、亞硝基亞氨基等）、氰基、氰酸基、腈基、亞 硝基、氮川基、磺基、磺醯基、亞磺基、磺酸基、锍基、 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -11 - 1283706 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明（9 ) 氨基甲醯基等（含水系媒體中有關此等的離子）此類可與 金屬離子配位的官能基僅具1個亦可，具2個以上（通通 常6個以下，理想爲4個以下）爲理想。此類具2個以上 官能基的水可溶性配位化合物形成成分，可列舉很多，其 中以使用有機酸爲理想。此有機酸如氨基酸（甘氨酸等的 氨基醋酸、丙氨酸等的氨基丙酸、半胱氨酸等的氨基巯基 丙酸、醯胺硫酸等）、乳酸、檸檬酸、酒石酸、蘋果酸、 丙二酸、草酸、琥珀酸、富馬酸及馬來酸等（含水系媒體 中有關此等的離子）。可單獨使用1種，同時使用2種以 上亦可。 此類水可溶性配位化合物形成成分，被硏磨物所含上 述金屬爲銅時，形成水可溶性配位化合物特別有效果。特 別是使用氨基酸爲理想，又，爲提高恢復硏磨速度的作用 以使用甘氨酸爲理想。 本發明洗淨硏磨襯墊用組成物中含有的此水可溶性配 位化合物的量，以洗淨硏磨襯墊用組成物全體爲1 0 0質 量％時，以0 . 01〜25質量％ (更理想爲0 . 1〜 20質量％，最理想爲0 . 5〜1 5質量％)爲理想。 又，本發明的洗淨硏磨襯墊用組成物，作爲上述水溶 性成分及水可溶性配位化合物形成成分等的溶媒，通常含 有水系溶媒。其他本發明洗淨硏磨襯墊用組成物，依必要 可含有P Η調整劑、界面活性劑等的各種添加劑。作爲 ρ Η調整劑可列舉如對甲苯磺酸、十二烷基苯磺酸、異戊 二烯磺酸、葡糖酸、乳酸、檸檬酸、酒石酸、蘋果酸、戊 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -12- 1283706 Α7 Β7 五、發明説明（1〇 一 、丙一酸、甲酸、草酸、號拍酸、富馬酸、馬來酸、 鄰苯二甲酸' 及苯甲酸等的有機酸，硝酸、硫酸及磷酸$ 的無機酸’甲基胺、乙基胺、乙醇胺等的有機鹽、氫氧化 鈉、氫氧化鉀、碳酸鈉等的無機鹽等，其中以有機酸、無 機酸、有機鹽爲理想。又，此等可單獨1種或2種以上糸II. 合使用。又’作爲界面活性劑可列舉如脂肪族胺鹽、脂肪 族銨鹽等的陽離子系界面活性劑，或脂肪酸鹼、烷醚羰酸 鹽等的羰酸鹽，烷基苯磺酸鹽、烷基萘磺酸鹽、α 一烯坫 磺酸鹽等的磺酸鹽，高級醇硫酸酯鹽、烷基醚硫酸鹽等的 硫酸鹽’烷基磷酸酯等的磷酸酯鹽等的陰離子系界面活性I 劑，或聚環氧乙烷烷基醚等的醚型、甘油酯的聚環氧乙烷 ί1283706 A7 B7 V. INSTRUCTIONS ") Technical field (please read the precautions on the back and fill out this page) This is the cleaning method for the composition of the honing pad and the honing pad. It relates to the composition and use of the honing pad which can reduce the consumption of the water-insoluble compound during the honing to cause the formation of the clogging and honing pad, and the honing efficiency. The cleaning method of the honing pad for the composition of the cleaning and polishing pad. The Ministry of Technology, the Ministry of Science and Technology, the Intellectual Property Office, the Consumer Cooperative, which prints the chemical mechanical honing used for the honing of the semiconductor substrate (hereinafter referred to as "CMP" Said, the honing pad-containing slurry (water-based dispersion) is honed at the interface between the honing pad and the surface to be honed. In this case, a porous material such as a polyurethane foam is used as the honing pad, and the honing speed is lowered due to gradual clogging of the honing chips and the like. Therefore, in order to restore the surface of the honing pad to C Μ P, a grinding step of honing surface renewal is performed. This sanding step is performed by bending a honing object (grinding material) such as a diamond powder to honing the surface of the lining. Known grinding steps are known as in situ sanding, and interval sanding. The former is a method of honing the range in which the honing pad is not honed, and the latter is a method of grinding the honing. Today's C Μ P is in situ sanded as necessary, and interval sanding is usually a must. At this time, each honing piece is honed for 5 to 30 seconds interval sanding. Therefore, there is a limit to increasing the yield of the product. Further, the interval sanding is only apparent for physical and supply cooling water. However, the effect of chemistry was not tried. In recent years, 曰本特开 2000-309796 discloses that the paper scale applies the Chinese National Standard (CNS) A4 specification (210x297 mm) -4- 1283706 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description ( 2) The technique of using a detergent composition containing an anionic surfactant in the interval grinding. However, this detergent composition can be widely used as a type of honed material, and it is difficult to be an optimum detergent composition depending on the components constituting the semiconductor substrate and the components contained in the mash. Further, as a slurry used for C Μ P, for example, Japanese Laid-Open Patent Publication No. Hei 8-83780, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei 11-16804, Japanese Patent Laid-Open No. Hei 11-116948, and Japanese Patent Laid-Open No. Hei 2 0 0 1 - 1 In order to prevent the metal constituting the honed surface from being excessively etched by the mash, or to prevent the honed metal from adhering to the honing surface again, it is proposed to use 硏 硏 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 The slurry contains a slurry which forms a water-insoluble component of a metal atom or an ion thereof separated by a honing surface. The use of such a slurry to eliminate C Μ Ρ 硏 衬垫 衬垫 , , , , , , , , 硏 硏 硏 硏 硏 硏 硏 硏 硏 inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter inter The consumption of honing pads is also intense and not ideal. DISCLOSURE OF THE INVENTION The present invention provides a solution for solving the above problems, at least washing a part of the honing water insoluble material formed on the surface of the honing pad, recovering the honing speed, and further suppressing the consumption of the honing pad. The net honing pad is intended for use with the composition. Further, it is possible to provide a cleaning method in which the honing pad is washed more efficiently by using the composition for cleaning the honing pad, and the lining pad can be improved in productivity and the lining pad can be suppressed from being consumed. purpose. (Please read the precautions on the back and fill out this page.) This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -5 - 1283706 A7 B7 _ V. Invention Description (3) The present invention is as follows . (Please read the precautions on the back and fill out this page.) 1. Composition of a cleaning honing pad characterized by water-soluble components that can dissolve water-insoluble compounds of metal atoms or their ions separated by the honed surface. Things. 2 · The above water-soluble component is composed of ammonia, potassium hydroxide, tetramethylammonium hydroxide, trimethyl-2-hydroxyethylammonium hydroxide, methyltrihydroxyethylammonium hydroxide, dimethyldicarboxylate A composition for a cleaning and honing pad according to any one of the above-mentioned one of at least one selected from the group consisting of hydroxylammonium hydroxide, tetraethylammonium hydroxide, and trimethylethylammonium hydroxide. 3. The metal is a composition for a cleaning honing pad described in the above 2, which is at least one selected from the group consisting of copper, aluminum, tungsten, and giant. 4. A composition for a cleaning and honing pad according to the above 1 which further comprises a water-soluble complex compound forming component which forms a water-soluble complex compound with the metal atom or an ion thereof. Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Co., Ltd. 5. The above water-soluble components are composed of ammonia, potassium hydroxide, tetramethylammonium hydroxide, trimethyl-2-hydroxyethylammonium hydroxide, and methylated hydroxide. A composition for cleaning the honing pad described in the above 4, which is at least one selected from the group consisting of ethylammonium, dimethyldihydroxyammonium hydroxide, tetraethylammonium hydroxide, and trimethylethylammonium hydroxide. A water-soluble complex compound-forming component comprising the above-mentioned five components for a cleaning and honing pad having two or more functional groups which are capable of coordinating with the metal atom and an ion thereof. 7. The above water-soluble coordination compound forming component is composed of glycine, alanine, cysteine, guanamine sulfuric acid, lactic acid, citric acid, tartaric acid. The paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). -6- 1283706 A7 B7 V. INSTRUCTION DESCRIPTION (4) The cleaning honing lining described in the above 6 of at least one selected from the group consisting of malic acid, malonic acid, oxalic acid, succinic acid, fumaric acid and maleic acid The pad is composed of a composition. 8 - The metal is at least one selected from the group consisting of copper, aluminum, tungsten, and tantalum. The composition for the cleaning and honing pad described in 7. 9. A method of washing a honing pad to which a water-insoluble compound containing metal atoms or ions separated by a honed surface is adhered, and contacting with a composition for washing a honing pad containing a water-soluble component of the water-insoluble compound A method of honing pad cleaning. 10. The water-soluble component is ammonia, potassium hydroxide, tetramethylammonium hydroxide, trimethyl-2-hydroxyethylammonium hydroxide, methyltrihydroxyethylammonium hydroxide, dimethyldicarboxylate A method of cleaning the honing pad described in the above 9 of at least one selected from the group consisting of hydroxylammonium hydroxide, tetraethylammonium hydroxide, and trimethylethylammonium hydroxide. 1 1 . The above-mentioned metal is a method of cleaning a honing pad described in the above 10, which is selected from at least one of copper, aluminum, tungsten and tantalum. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. 12. The above-mentioned nine methods of washing the honing pad, which contain a water-soluble complex compound forming component which forms a water-soluble complex compound with the above metal atom or its ion. 13. The above water-soluble component is ammonia, potassium hydroxide, tetramethylammonium hydroxide, trimethyl-2-hydroxyethylammonium hydroxide, methyltrihydroxyethylammonium hydroxide, dimethyldicarboxylate A method of cleaning the honing pad described in the above 12, which is at least one selected from the group consisting of hydroxylammonium hydroxide, tetraethylammonium hydroxide, and trimethylethylammonium hydroxide. 1 4 . The above water-soluble coordination compound forming component, which has two paper scales applicable to China National Standard (CNS) A4 specification (21〇X297 mm) 1283706 A7 B7 5. Inventive Note (5) The above functional groups can be The method for cleaning a honing pad described in the above 13 of the above-mentioned metal atom and its ion. (Please read the precautions on the back and fill out this page) 1 5 · The above water-soluble coordination compound forms components, which are glycine, alanine, cysteine, guanamine sulfuric acid, lactic acid, citric acid, tartaric acid, apple A method of washing a honing pad described in the above-mentioned item 4, which is at least one selected from the group consisting of acid, malonic acid, oxalic acid, succinic acid, fumaric acid, and maleic acid. The above-mentioned metal is a method of cleaning a honing pad described in the above 15th, which is selected from at least one of copper, aluminum, tungsten and rhenium. According to the cleaning composition for a honing pad and the lining pad of the present invention, the honing pad used for honing can be released from the honed surface, and the water formed by ionizing the metal ions The clogging formed by the insoluble compound can restore the honing speed, suppress the consumption of the honing pad, and improve the productivity. The composition for a cleaning honing pad of the present invention contains a water-soluble component and is characterized by being water-soluble in a water-insoluble compound of a metal atom or an ion thereof separated by a honing surface. The "metal" printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs is not particularly limited, and examples thereof include copper, aluminum, tungsten, molybdenum, giant, titanium, indium, and tin. One type of the metal, or two or more types may be used. 'The valence of ions is also unlimited. The above-mentioned metal used in the composition for cleaning the honing pad of the present invention is also particularly effective in at least one selected from the group consisting of aluminum, tungsten and giant. Further, the above-mentioned "honed surface" base material constituting a separation source of a metal atom or an ion thereof may, for example, be a metal alloy or an alloy (such as a copper-lauric alloy or a copper-aluminum alloy). Therefore, the process of separating the honing surface is not particularly limited, and the ionized surface of the honed surface is ionized by the acid or oxidant contained in the mash, and the size of the paper is applied to the Chinese National Standard (CNS) A4 specification (210x297 Gongdong^ 1283706 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees' Consumer Cooperatives Printed V. Inventive Note (6) It is also possible to combine it with a water-insoluble compound-forming component contained in the slurry as described later. The substrate supporting the honing surface is not particularly limited, and various substrates may be used, and examples thereof include a semiconductor substrate, a glass substrate for LCD, and a glass substrate for TFT. The "water-insoluble compound" is insoluble in honing. A compound in which a solid component remains on the honing surface of the honing pad, such as mash, but also a poorly water-soluble compound which is not completely dissolved in water and is slightly soluble in water. The solubility of the water-insoluble compound is not particularly high. The limitation generally refers to a compound of p Η 1 to 1 2, at any temperature between 1 5 and 5 0 ° C, below 1 g / 100 g of water. In particular, the above metal is the pH of copper 7 ~1 At 1 o'clock, when the pH of aluminum is 2 to 6, when the pH of the tungsten is 2 to 6, and when the pH is 3 to 1 of hydrazine, the solubility is easily less than 1 g / 1 〇〇g of water. Further, the water-insoluble compound is one kind. The water-insoluble compound forming component which forms the compound is not particularly limited, and examples thereof include a hydroxyl group, an alkoxy group (methoxy group, ethoxy group, etc.), a carboxyl group, and a carbonyl group (methoxycarbonyl group, Ethoxycarbonyl group, etc., amino group (containing a first amino group, a second amino group, a third amino group, a hydroxyamino group, a nitroamino group, a nitrosoamino group, etc.), an imino group (containing a fluorenyl group, a hydroxyimino group, Sulfoimino, nitro-amino, nitrosomino, etc.), cyano, cyanate, nitrile, nitroso, nitroso, sulfo, sulfonyl, sulfinyl, sulfonate And a thiol group, a carbhydryl group, etc. (the ion in the aqueous medium) has a compound containing a nitrogen, oxygen, and sulfur functional group, and an aromatic compound or a heterocyclic compound having such a functional group, or Hetero condensed ring (please read the note on the back and fill out this page) National Standard (CNS) A4 Specification (210X297 mm) -9- 1283706 Α7 Β7 V. Inventive Note (7) Compound (especially a fused ring compound with a heterocyclic ring or a condensed cyclized product with a heterocyclic ring). First, please read the precautions on the back side and fill out this page. Specific examples of the component which forms a water-insoluble compound include pyrazine, pyridine, pyrrole, pyridazine, histidine, thiophene, triazine heterocycle, toluene triazacyclocycle. , hydrazine, benzimidazole, benzotriazane, benzofuran, benzoxazole, benzoquinone, benzothiazole, quinoline, quinoxaline, quinazoline, p-benzoquinone, benzoquinone Derivative compounds such as pyridine, benzopyran, benzoxazine and melamine (particularly, derivative compounds having the above functional groups), salicylaldoxime, cupferron, sulfonic acid and the like. Further, the water-insoluble compound is not only a product of a water-insoluble compound forming component and copper as described above, but also a copper oxide which is oxidized by an oxidizing agent contained in the honing slurry. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives Co., Ltd. The above-mentioned "water-soluble component" is a component that dissolves the above-mentioned insoluble compound in water. Thus, the water-soluble component and the water-insoluble compound are preferably impregnated with water by water immersed in the surface of the honing pad or water immersed in the lining pad. Examples of such water-soluble components include ammonia, potassium hydroxide, and oxidized fourth-order ammonium {hydrogen tetramethylammonium (TMAH), trimethyl-2-hydroxyethylammonium hydroxide, and methyltrihydroxyl hydroxide. Ethyl ammonium, dimethyldiammonium hydroxide, tetraethylammonium hydroxide, trimethylethylammonium hydroxide, etc. (including such ions in aqueous media). Among them, it is desirable to use ammonia and/or T M A Η. One such water-soluble component may be used alone or in combination of two or more. In addition, such a water-soluble component may have at least one of the above-mentioned metal copper, indium, tungsten, and giant, and may dissolve the compound in an effective manner. The metal is a copper-based paper scale applicable to the Chinese National Standard (CNS) Α4 specification ( 210Χ297 mm) -10 - 1283706 A7 B7 V. The invention description (8) is particularly desirable. (Please read the precautions on the back side and fill out this page.) The composition for cleaning the honing pad of the present invention contains the water-soluble component in an amount of not particularly limited, and the composition for cleaning the honing pad of the present invention is When it is 100% by mass, it is preferably 0. 0 1 to 20% by mass (ideally 0.1 to 15% by mass, more preferably 0 to 5 to 10% by mass). Further, the composition for cleaning the honing pad of the present invention is preferably a component containing a metal atom or an ion thereof and a water-soluble coordination compound which forms a water-soluble complex compound. The above "water-soluble complex compound" is easily soluble in water and can be sufficiently dissolved in a water complex. The solubility of the water-soluble complex compound is not particularly limited as long as it exceeds the solubility of the water-insoluble compound under the same measurement conditions. In addition, the above-mentioned "water-soluble complex compound forming component" and the metal ion coordination form a water-soluble coordination compound can be produced by one or more of the complex compounds. ingredient. Usually, the water-soluble coordination compound forms a component having a functional group coordinated to a metal ion. It is desirable that the g group contains at least one of nitrogen, oxygen and sulfur. Such a functional group may be, for example, a hydroxyl group, an alkoxy group (methoxy group, an ethoxy group, etc.), a carboxyl group, a carbonyl group (methoxycarbonyl group, an ethoxycarbonyl group, etc.), an amino group (containing a first-order amino group, a second amino group, a third amino group, a hydroxyamino group, a nitroamino group, a nitrosoamino group, etc.), an imino group (including a B group, a carbimimino group, a sulfomino group, a nitro-amino group, a nitroso group) Amino, etc.), cyano, cyanate, nitrile, nitroso, nitrilo, sulfo, sulfonyl, sulfinyl, sulfonate, sulfhydryl, this paper scale applies to Chinese National Standard (CNS) A4 size (210 X 297 mm) -11 - 1283706 Α7 Β7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (9) carbamate, etc. (related to such ions in aqueous media) It is also possible to have only one functional group that can be coordinated with a metal ion, and it is preferable to have two or more (normally six or less, preferably four or less). Such a water-soluble complex compound having two or more functional groups may be a component, and many of them may be used, and an organic acid is preferably used. The organic acid is, for example, an amino acid (aminoacetic acid such as glycine, aminopropionic acid such as alanine, aminomercaptopropionic acid such as cysteine, or guanamine sulfuric acid), lactic acid, citric acid, tartaric acid, malic acid, and propylene glycol. Acid, oxalic acid, succinic acid, fumaric acid, maleic acid, etc. (related to such ions in aqueous media). One type can be used alone, and two or more types can be used at the same time. Such a water-soluble coordination compound forms a component, and when the metal contained in the honed material is copper, it is particularly effective to form a water-soluble coordination compound. In particular, the use of amino acids is ideal, and in order to improve the recovery of honing speed, it is desirable to use glycine. 01〜25质量质量。 When the amount of the composition of the honing pad is 100% by mass, the total amount of the water-soluble complex compound is 0.001% by mass. (More preferably 0. 1~20% by mass, most preferably 0. 5~1 5 mass%) is ideal. Further, the composition for cleaning the honing pad of the present invention usually contains a water-based solvent as a solvent for the water-soluble component and the water-soluble complex compound forming component. In the other composition for cleaning the honing pad of the present invention, various additives such as a P Η adjusting agent and a surfactant may be contained as necessary. Examples of the ρ Η adjusting agent include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, isoprenesulfonic acid, gluconic acid, lactic acid, citric acid, tartaric acid, malic acid, and pentane (please read the back of the back). Please fill in this page again. This paper size is applicable to China National Standard (CNS) Α4 specification (210Χ297 mm) -12- 1283706 Α7 Β7 5. Description of invention (1〇1, propionate, formic acid, oxalic acid, acethanide, Organic acids such as fumaric acid, maleic acid, phthalic acid and benzoic acid, organic salts of nitric acid, sulfuric acid and phosphoric acid, such as 'methanolamine, ethylamine and ethanolamine, sodium hydroxide and hydrogen An inorganic salt such as potassium oxide or sodium carbonate is preferably an organic acid, an inorganic acid or an organic salt. Further, these may be used alone or in combination of two or more kinds of ruthenium II. a cationic surfactant such as an aliphatic amine salt or an aliphatic ammonium salt, or a carboxylate such as a fatty acid base or an alkyl ether carbonate, an alkylbenzenesulfonate, an alkylnaphthalenesulfonate, or a a sulfonate such as an enesulfonate, a higher alcohol sulfate, or an alkyl ether sulfur Sulfate salts of 'such as alkyl phosphate ester salt anionic surfactant such agents I, or polyethylene oxide alkyl ethers such as ether type, polyoxyethylene glycerides ί
I 醚等的醚酯型、聚乙二醇脂肪酸酯、甘油酯、山梨糖醇酷 、等的酯型非離子系界面活性劑等。適當的添加此等界而 活性劑，不僅增大水不溶性化合除去的效率，有效率的除 去硏磨中發生的硏磨屑或硏磨硏漿中殘留的硏磨粒。 經濟部智慧財產局員工消費合作社印製 本發明洗淨硏磨襯墊用組成物的ρ Η，以具有高於硏 磨步驟的硏磨硏漿的ρ Η爲理想，通常爲8以上，被硏磨 面的構成金屬爲鋁或鎢時爲9以上，銅或鉅時以超過1 1 爲更理想。 . 依本發明的洗淨硏磨襯墊用組成物，C Μ Ρ使用的硏 磨襯墊所形成上述的水不溶性化合物，硏磨面的阻塞確寶 的解消了，可恢復硏磨速度。此時進行打磨亦可，不進行 亦可，以進行打磨的硏磨面更可確實的再生爲理想。此卟 使用本發明的洗淨硏磨襯墊用組成物可抑制因打磨所引起 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -13- 1283706 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（11 ) 的硏磨襯墊的消耗，更可提高生產性（Thru-put)。 本發明的硏磨襯墊洗淨方法，係洗淨附著有由被硏磨 面所分離的含金屬原子或其離子的水不溶性化合物的硏磨 襯墊的方法，使硏磨襯墊與上述洗淨硏磨襯墊用組成物接 觸爲其特徵。 有關本發明的洗淨方法，使硏磨襯墊與上述洗淨硏磨 襯墊用組成物接觸的方法無特別限定，可使用種種的方法 。例如，將洗淨硏磨襯墊用組成物滴入硏磨表面，可用高 壓噴霧噴射。更可將硏磨襯墊本身浸漬於洗淨硏磨襯墊用 組成物中。 又，硏磨襯墊與洗淨硏磨襯墊用組成物接觸時，可同 時加入其他的物理的力量。即，上述以滴入供給時，以裸 基板（不具金屬部基板）化替半導體基板，以裸基板摺動 硏磨襯墊。又，可倂用向來的打磨。更且，可用刷子刷拭 硏磨襯墊表面。又，浸漬.接觸時，可用產生高壓流與硏磨 襯墊表面踫撞以外，亦可以超音波輔助。 使用本發明的洗淨方法，以1 〇 〇〜1 〇 〇 c c /分 鐘的速度供給本發明的洗淨硏磨襯墊用組成物，加於打磨 負荷的荷重以3 0〜2 0 0 N同時進行間歇打磨，由停止 硏磨至硏磨襯墊洗淨完了的時間可在1 0秒至5分鐘，又 ，依本發明的洗淨方法，可大幅抑制硏磨襯墊的消耗，又 ，所定時間內可硏磨的被硏磨物的數量可增加，即可提高 硏磨生產性。又，如本發明有關的對象，由水不溶性化合 物的阻塞的硏磨襯墊的硏磨性能，以向來的機械間歇打磨 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -14 - 1283706 A7 B7 五、發明説明（12 ) (請先閲讀背面之注意事項再填寫本頁) 來恢復時，通常需要1 〇分鐘以上。因此，不僅生產效率 有問題，對硏磨襯墊的壽命亦有不良的影響，不能提供實 際使用。 依本發明的硏磨襯墊洗淨方法，硏磨襯墊的恢復率， 可達8 8%以上，更理想爲9 0%以上。 圖面之簡單說明 【圖1】 由實施例所得，顯示基板的硏磨片數與硏磨速度的相 關圖表。 主要元件對照表 1 硏磨速度 2 基板硏磨片數 發明之最佳實施形態 以下使用實施例更詳細說明本發明。 經濟部智慧財產局員工消費合作社印製 〔1〕硏漿的調製 (1 )硏漿s 1 全體爲100質量份（以下簡稱爲「份」）時，以離子 交換水9 3 . 2份，氫氧化0 . 2份，喹哪啶酸（水不溶 性化合物形成成分）0 . 5份，平均一次粒徑1 2 n m， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -15- 1283706 A7 B7 五、發明説明（13 ) (請先閱讀背面之注意事項再填寫本頁) 平均粒徑2 0 0 n m的膠質二氧化硅5 · 0份，十二院基 苯磺酸銨0 . 1份，過硫酸錢1 · 0份配合後，擾拌3小 時得到硏漿Si，所得之硏漿Si的pH爲7 · 2。 (2 )硏漿S 2 全體爲100質量份（以下簡稱爲「份」）時，以離 子交換水95.5份，氨〇.15份，平均一次粒徑3〇 nm，平均粒徑2 0 0 nm的膠質二氧化3 . 5份，十二 院基苯磺酸銨0 · 1份，過氧化氫0 · 3份，配合後，攪 拌3小時得到硏漿S 2，所得之硏漿S !的p Η爲7 . 6。 〔2〕洗淨硏磨襯墊用組成物的調製 洗淨硏磨襯墊用組成物Α〜Η ( Α〜G :本發明品，η : 比較品） 經濟部智慧財產局員工消費合作社印製 各洗淨硏磨襯墊用組成物爲1 0 0份時，如表1所示 水溶化成分及水性配位化合物形成成分的依表1所示比例 ，剩餘爲離子交換水配合之後，攪拌3小時得到洗淨硏磨 襯墊用組成物Α〜F， 又，洗淨硏磨襯墊用組成物爲1 0 0份時，僅水溶化 成分，或僅水性配位化合物形成成分如表依表1所示比例 ，剩餘爲離子交換水配合之後，攪拌3小時得到洗淨硏磨 襯墊用組成物G及Η。又，表1所示之「氨」爲乾淨的^ 氨」。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -16- 1283706 A7 B7 五 .、發明説明（14 ) 洗淨硏磨襯墊用 組成物 水溶化成分 水可溶性配ίί 〆 〔化合物形成成 pH 種類 配合比例 種類 配合比例 (份） (份） A 甘氨酸 5 11.0 B 丙氨酸 11.1 C 氨 5 孔酸 10.1 D 檸檬酸 10 9.9 E 琥珀酸 10.2 F ΤΜΑΗ 5 甘氨酸 5 9.9 G 氨 5 - >14 Η - 甘氨酸 5 6.3 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 〔3〕有關於連續硏磨之硏磨速度（參考例） 使用〔1〕所得的硏漿S i，以覆蓋膜厚6 0 0 0 A 上銅基板作爲被硏磨物（構成被硏磨面的金屬：銅），5 磨連續的2 5片基板（即硏磨間不進行間歇打磨）。此 CMP裝置（日本株式會社荏原製作所製，型式「EP( —1 1 2」）使用的定盤，貼上多孔質聚氨基甲酸乙酯| 的硏磨襯墊（r〇DELL KNITTER公司製，商品名 1 C 1 〇 〇 0 )。又，依硏漿s 1的供給速度爲每分鐘 2〇〇cc，基板載體的荷重爲1〇5 hPa，轉盤E 轉數爲iOOrpm，硏磨頭回轉數爲1〇1 rp ) Μ規格（21GX297公釐） -17- 1283706 A7 B7 五、發明説明（15 ) 條件進行。各基板進行1分鐘的硏磨。 在進行硏磨中，算出各基板的硏磨速度，其結果如圖 1所示。又，此時的硏磨速度係依下述式（1 )算出。又 式（1 )中之銅膜的厚度係依電阻率測定機（N P S製， 型式「Σ - 1 0」）所測定的電阻値與銅膜的電阻率（文 獻値）以下述式（2 )算出。 硏磨速度（A/min) = (硏磨前的銅膜的厚度-硏磨後的銅膜 的厚度）/硏磨時間......(1) 銅膜的厚度（A) = {電阻値（Ω/cm2) X銅膜的電阻率（Ω/cm)} xlO8......(2) 〔4〕有關洗淨硏磨襯墊用組成物的效果 (1 )基板的硏磨 與〔3〕同樣，使用硏漿Si或硏漿S2，以覆蓋膜厚 6000 A以上銅基板作爲被硏磨物（構成被硏磨面的金 屬：銅），以〔3〕同樣的硏磨條件硏磨連續的2 3片基 板。基於此硏磨，算出第1片基板的硏磨速度（v F )與第 2 3片基板的的硏磨速度，如表2所示。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ! 壤— (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -18- 1283706 A7 B7 五、發明説明（16 ) 經濟部智慧財產局員工消費合作社印製 表2 使用硏漿 洗淨硏磨 第1片的硏磨 第23片的 洗淨後第1片 恢復率 襯墊用組 速 度 硏磨速度 的硏磨速度 Vl/Vf 成物 VF(A/min) (A/min) Vl( A/min) x 100 1 Si A 6650 5690 6520 98.0 實 2 S2 6480 5480 6700 103.4 施 3 Si B 6380 5620 6410 100.5 例 4 .S2 6600 5520 6220 94.2 5 Si C 6460 5630 6100 94.4 6 S2 6570 5590 6220 94.7 7 Si D 6480 5720 6280 96.9 8 S2 6520 5780 6250 95.9 9 Si E 6500 5850 6220 95.7 10 S2 6690 5780 6340 94.8 11 Si F 6410 5300 6100 95.2 12 S2 6290 5450 6090 96.8 13 Si G 6620 5610 6040 91.2 比較例1 Si H 6430 5470 5580 86.8 (請先閱讀背面之注意事項再填寫本頁)An ester type nonionic surfactant such as an ether type such as ether, a polyethylene glycol fatty acid ester, a glycerin ester, or a sorbitol. Appropriate addition of such an active agent not only increases the efficiency of water-insoluble removal, but also effectively removes the honing particles occurring in the honing or the honing particles remaining in the mash.智慧 印 组成 员工 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济 经济When the constituent metal of the ground surface is aluminum or tungsten, it is 9 or more, and copper or giant time is more preferably more than 1 1 . According to the composition for cleaning the honing pad of the present invention, the above-mentioned water-insoluble compound is formed by the honing pad used in C Μ , and the occlusion surface is removed, and the honing speed can be restored. At this time, it is also possible to perform the grinding, and it is also possible to carry out the grinding, and the honing surface to be polished can be reliably regenerated. In this case, the composition for the cleaning honing pad of the present invention can be used to suppress the paper size applicable to the Chinese National Standard (CNS) Α4 specification (210×297 mm) -13- 1283706 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau The consumption of the honing pad by the employee consumption cooperative, the invention description (11), can improve the productivity (Thru-put). The honing pad cleaning method of the present invention is a method of washing a honing pad to which a water-insoluble compound containing a metal atom or an ion thereof, which is separated by a honed surface, is attached, and the honing pad is washed with the above The net honing pad is characterized by contact with the composition. In the cleaning method of the present invention, the method of bringing the honing pad into contact with the composition for cleaning the honing pad is not particularly limited, and various methods can be used. For example, the composition of the washed honing pad is dropped onto the honing surface and sprayed with a high pressure spray. Further, the honing pad itself can be immersed in the composition for washing the honing pad. Further, when the honing pad is in contact with the composition for cleaning the honing pad, other physical forces can be added at the same time. That is, when the supply is dripped, the semiconductor substrate is replaced by a bare substrate (without a metal portion substrate), and the pad is honed with a bare substrate. Also, you can use the polished ones. Also, the surface of the pad can be honed with a brush. Further, in the case of immersion and contact, it is possible to use a high-pressure flow to collide with the surface of the honing pad, and it is also possible to assist by ultrasonic waves. By using the cleaning method of the present invention, the composition for cleaning the honing pad of the present invention is supplied at a rate of 1 〇〇 to 1 〇〇 cc / minute, and the load applied to the grinding load is 3 0 to 2 0 0 N simultaneously. For intermittent grinding, the time from the stop honing to the honing pad cleaning can be from 10 seconds to 5 minutes. Moreover, according to the cleaning method of the present invention, the consumption of the honing pad can be greatly suppressed, and The amount of honed objects that can be honed in time can be increased to improve the honing productivity. Further, as the object of the present invention, the honing performance of the honing pad which is blocked by the water-insoluble compound is mechanically polished in the past (please read the back sheet of the precautions and fill in the page). The paper size is applicable to the Chinese country. Standard (CNS) A4 size (210X297 mm) -14 - 1283706 A7 B7 V. Invention description (12) (Please read the note on the back and fill out this page). It usually takes more than 1 minute to recover. Therefore, not only the production efficiency is problematic, but also the life of the honing pad is adversely affected, and the actual use cannot be provided. According to the honing pad cleaning method of the present invention, the recovery rate of the honing pad can be up to 88% or more, more preferably more than 90%. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a graph showing the number of honing sheets of a substrate and the honing speed obtained from the examples. Main component comparison table 1 honing speed 2 number of substrate honing sheets BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail by way of examples. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumers Cooperatives. [1] Preparation of mash (1) When the whole slag s 1 is 100 parts by mass (hereinafter referred to as "parts"), ion exchange water is 9.3 parts, hydrogen Oxidized 0.2 parts, quinaldic acid (water-insoluble compound forming component) 0.5 parts, average primary particle size 12 nm, the paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -15- 1283706 A7 B7 V. INSTRUCTIONS (13) (Please read the note on the back and then fill out this page.) The average particle size of 2 0 0 nm of colloidal silica 5 · 0 parts, 12 - yard ammonium benzenesulfonate 0. After 1 part of the persulfate money, the mixture was stirred for 3 hours to obtain a slurry of Si, and the pH of the obtained slurry Si was 7.2. (2) When the whole slurry S 2 is 100 parts by mass (hereinafter referred to as "parts"), 95.5 parts of ion-exchanged water, 15 parts of ammonia hydrazine, an average primary particle diameter of 3 〇 nm, and an average particle diameter of 2 0 0 nm The colloidal dioxide was 3.5 parts, the twelfth yard ammonium benzenesulfonate 0. 1 part, and the hydrogen peroxide 0 · 3 parts. After mixing, stirring for 3 hours to obtain the slurry S 2 , the obtained slurry S ! Η is 7.6. [2] Preparation of the composition for washing and honing the padding Washing the composition for the honing pad Α~Η ( Α~G: The present invention, η: Comparative product) Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative When the composition for each of the cleaning honing pads is 100 parts, the ratio of the water-soluble component and the aqueous complex compound forming component shown in Table 1 is as shown in Table 1, and the remainder is ion-exchanged water, and then stirred. When the composition of the honing pad is Α~F is obtained in an hour, and the composition for washing the honing pad is 100 parts, only the water-soluble component or only the aqueous complex compound is formed as a table. In the ratio shown in Fig. 1, after the remaining ion-exchanged water was mixed, the mixture was stirred for 3 hours to obtain a composition for cleaning the honing pad G and hydrazine. Further, the "ammonia" shown in Table 1 is a clean ammonia. This paper scale is applicable to China National Standard (CNS) Α4 specification (210Χ297 mm) -16- 1283706 A7 B7 V., invention description (14) Washing honing pad composition water-soluble component water-soluble ίί 〆 [compound Forming into a pH type, mixing ratio, proportion (parts) (part) A glycine 5 11.0 B alanine 11.1 C ammonia 5 hole acid 10.1 D citric acid 10 9.9 E succinic acid 10.2 F ΤΜΑΗ 5 glycine 5 9.9 G ammonia 5 - > ;14 Η - Glycine 5 6.3 (Please read the notes on the back and fill out this page) Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs [3] About the honing speed of continuous honing (Reference example) Use [1] The obtained slurry S i is covered with a copper substrate of a film thickness of 600 Å as a honed object (metal constituting the surface to be honed: copper), and 5 continuous substrates of 5 pieces (ie, honing is not Perform intermittent grinding). This CMP apparatus (manufactured by Ebara Seisakusho Co., Ltd., a type of "EP (-1 1 2"), is a lapper pad made of porous polyurethane (made by r〇DELL KNITTER). Name 1 C 1 〇〇 0 ). Further, the supply speed of the slurry s 1 is 2 〇〇 cc per minute, the load of the substrate carrier is 1 〇 5 hPa, the number of revolutions of the turntable E is iOO rpm, and the number of revolutions of the honing head is 1〇1 rp ) Μ Specifications (21GX297 mm) -17- 1283706 A7 B7 V. Description of invention (15) Conditions are carried out. Each substrate was subjected to honing for 1 minute. In the honing, the honing speed of each substrate was calculated, and the results are shown in Fig. 1. Moreover, the honing speed at this time is calculated by the following formula (1). Further, the thickness of the copper film in the formula (1) is determined by the following formula (2): the electric resistance of the electric resistance 値 and the copper film measured by a resistivity measuring machine (manufactured by NPS, type "Σ - 10"). Calculated. Honing speed (A/min) = (thickness of copper film before honing - thickness of copper film after honing) / honing time... (1) Thickness of copper film (A) = { Resistance 値 (Ω/cm2) X Resistivity of copper film (Ω/cm)} xlO8 (2) [4] Effect on the composition of the honing pad (1) In the same manner as in [3], the squeegee Si or the squeegee S2 is used to cover the copper substrate having a thickness of 6000 A or more as the honed object (the metal constituting the honed surface: copper), and the same honing is performed [3]. Conditions honed two consecutive 2 substrates. Based on this honing, the honing speed (v F ) of the first substrate and the honing speed of the second substrate were calculated as shown in Table 2. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm)! Soil - (Please read the note on the back and fill out this page) Order Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed -18- 1283706 A7 B7 V. INSTRUCTIONS (16) Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumers Cooperatives, Printed Table 2: Using the mash to clean the first piece of the honing of the 23rd piece after the first piece of recovery rate padding group speed 硏Honing speed of grinding speed Vl/Vf Product VF(A/min) (A/min) Vl( A/min) x 100 1 Si A 6650 5690 6520 98.0 Real 2 S2 6480 5480 6700 103.4 Application 3 Si B 6380 5620 6410 100.5 Example 4 .S2 6600 5520 6220 94.2 5 Si C 6460 5630 6100 94.4 6 S2 6570 5590 6220 94.7 7 Si D 6480 5720 6280 96.9 8 S2 6520 5780 6250 95.9 9 Si E 6500 5850 6220 95.7 10 S2 6690 5780 6340 94.8 11 Si F 6410 5300 6100 95.2 12 S2 6290 5450 6090 96.8 13 Si G 6620 5610 6040 91.2 Comparative Example 1 Si H 6430 5470 5580 86.8 (Please read the notes on the back and fill out this page)
本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -19- 1283706 A7 B7 五、發明説明（17 ) (2 )硏磨襯墊的洗淨及打磨（實施例） (請先閲讀背面之注意事項再填寫本頁) 續之，在進行第2 4片基板的硏磨，於基板載體安裝 裸硅基板，以每分鐘2 0 0 c c的速度供給〔2〕所得的 各洗淨硏磨襯墊用組成物A〜G，轉盤回轉數爲7 0 rpm，基板載體的荷重爲300hPa，硏磨頭回轉數 爲7 〇 r p m的條件進行2分鐘的硏磨襯墊洗淨。此時’ 於硏磨襯墊上基板載體不存在的範圍，以外徑2 7 0 m m 的# 1 Ο 0鑽石打磨劑，打磨回轉數2 5 r p m，打磨荷 重1 Ο 0 h P a，使硏磨襯墊摺動進行間歇打磨。其後， 立即以每分鐘6 0 0 c c的速度供給離子交換水進行1分 鐘的水洗。 (3 )硏磨襯墊的洗淨及打磨（比較例） 使用S i作爲硏漿，用Η作爲洗淨硏磨襯墊用組成物， 除不使用打磨劑外，與上述（2 )同樣，進行硏磨襯墊的 洗淨及水洗。 經濟部智慧財產局員工消費合作社印製 (4 )硏磨襯墊的洗淨效果 使用上述的已硏磨襯墊的洗淨完了的硏磨襯墊，與（ 1 )同樣進行第2 4片基板的硏磨1分鐘。算出此第2 4 片基板的硏磨速度，倂記於表2。又，由第1片基板的硏 磨速度（Vf)及第2 4片基板的硏磨速度（Vl)算出（ V L ) / ( V F ) X 1 0 0作爲恢復率，倂記於表2。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -20- 1283706 Α7 Β7 五、發明説明（18 ) (5 )結果 由〔3〕的圖1的結果，可知有關形成水不溶性化合 物基板的硏磨，硏磨片數1 0片程度槪略保持初期的硏磨 速度（6500A/min)，至第15片程度硏磨速度 逐漸開始下降，超過2 0片時硏磨速度急速下降（第2 5 片爲初期的硏磨速度降低1 0 0 0 A/m i η )。 對此，由〔4〕的相關的表2結果，如〔3〕的結果 硏磨連續進行2 0片以上基板的硏磨速度降低的硏磨襯墊 ，使用賢施例1〜1 3本發明的洗淨硏磨組成物進行洗淨 時，知道約略可完全恢復至初期的硏磨速度（恢復率 9 4 _ 2 %以上）。特別是，實施例1及2所示使用氨爲 水溶化成分，且使用甘氨酸作爲水可溶性配位化合物形成 成分時，恢復率達9 8 %以上，知道可獲得優異效果。相 對，可知比較例的恢復率爲8 6 . 8 %與實施例1〜1 3 比較時較差。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -21 -This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -19- 1283706 A7 B7 V. Invention description (17) (2) Washing and polishing of honing pad (Example) (Read first Note on the back side. Fill in this page. Continued, the honing of the 24th substrate is performed, and the bare silicon substrate is mounted on the substrate carrier, and the cleaning 〔 obtained in [2] is supplied at a rate of 200 cc per minute. For the polishing pad compositions A to G, the number of revolutions of the turntable was 70 rpm, the load of the substrate carrier was 300 hPa, and the number of revolutions of the honing head was 7 rpm, and the honing pad was washed for 2 minutes. At this time, in the range where the substrate carrier does not exist on the honing pad, the #1 Ο 0 diamond grinding agent with an outer diameter of 270 mm, the number of revolutions is 2 5 rpm, and the grinding load is 1 Ο 0 h P a to make the honing The pad is folded for intermittent sanding. Thereafter, ion-exchanged water was immediately supplied at a rate of 60 c c per minute for 1 minute of water washing. (3) Washing and polishing of the honing pad (Comparative Example) Using S i as the mash and using hydrazine as the composition for the honing pad, the same as (2) above except that the polishing agent is not used. Wash and wash the honing pad. Printed by the Ministry of Economic Affairs, Intellectual Property Office, and the Consumer Cooperatives. (4) Washing effect of the honing pad. Using the honed pad of the honed pad described above, the 24th substrate is the same as (1). Pondering for 1 minute. The honing speed of the 24th substrate was calculated and described in Table 2. Further, the recovery rate (V L ) / ( V F ) X 1 0 0 was calculated from the honing speed (Vf) of the first substrate and the honing speed (Vl) of the second substrate as shown in Table 2. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -20- 1283706 Α7 Β7 V. Invention description (18) (5) Results From the results of Figure 3 of [3], it is known that the formation of water-insoluble compounds The honing of the substrate, the number of honing pieces is 10 pieces, and the initial honing speed (6500A/min) is maintained slightly. The honing speed gradually decreases from the 15th piece, and the honing speed drops sharply when it exceeds 20 pieces ( The 25th piece reduces the initial honing speed by 1 000 A/mi η ). On the other hand, from the result of Table 2 related to [4], as a result of [3], the honing pad which continuously reduces the honing speed of 20 or more substrates is honed, and the invention is used in the case of the application examples 1 to 13. When the washed honing composition is washed, it is known that the approximate honing speed can be completely restored to the initial honing rate (recovery rate of 9 4 _ 2 % or more). In particular, when ammonia is used as the water-soluble component and the glycine is used as the water-soluble complex compound-forming component as shown in Examples 1 and 2, the recovery rate is 98% or more, and it is known that an excellent effect can be obtained. In contrast, it was found that the recovery ratio of the comparative example was 86.8%, which was inferior to those of Examples 1 to 13. (Please read the notes on the back and fill out this page.) Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives. This paper scale applies to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) -21 -